CN104078698A - Molten carbonate fuel cell electrolyte storage and compensation method - Google Patents
Molten carbonate fuel cell electrolyte storage and compensation method Download PDFInfo
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- CN104078698A CN104078698A CN201410304820.XA CN201410304820A CN104078698A CN 104078698 A CN104078698 A CN 104078698A CN 201410304820 A CN201410304820 A CN 201410304820A CN 104078698 A CN104078698 A CN 104078698A
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- electrode
- barrier film
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/14—Fuel cells with fused electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/14—Fuel cells with fused electrolytes
- H01M2008/147—Fuel cells with molten carbonates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to a molten carbonate fuel cell electrolyte storage and compensation method. The method comprises the following steps: 1. preparing an electrode and a diaphragm as required, wherein the porosity of the electrode is 60-80% and the porosity of the diaphragm is 50-60%; 2. calculating the masses of Li2CO3 and K2CO3 molten salt electrolytes with molar ratio of 62 to 38 in a pore, required by the prepared electrode and the diaphragm after completely roasting; 3. fully and uniformly mixing the molten salt electrolytes after mass calculation, drying, and uniformly spreading the molten salt electrolytes on the electrode and the diaphragm respectively; 4. putting the electrode and the diaphragm with the molten salt electrolytes into a muffle furnace for roasting for 10-20h at 480-540 DEG C, storing the electrolytes required by the molten carbonate fuel cell in the electrode and the diaphragm, wherein the electrolytes stored in the electrode can compensate the diaphragm during cell running, so that the cell can run stably. The method is easy to operate and has the important significance on electrolyte storage and compensation of the improved molten carbonate fuel cell.
Description
Technical field
The present invention relates to molten carbonate fuel cell technical field, be specifically related to a kind of storage and compensation method of molten carbonate fuel cell electrolyte.
Background technology
Fuel cell is a kind ofly without burning, in electrochemical reaction mode, the chemical energy of fuel directly to be become to the Blast Furnace Top Gas Recovery Turbine Unit (TRT) of electric energy, its maximum feature is that course of reaction does not relate to burning, therefore energy conversion efficiency is not subject to the restriction of " Carnot cycle ", and efficiency is up to 50%～60%.Molten carbonate fuel cell (MCFC) is a kind of high-temperature fuel cell growing up in later stage the 1950's, and working temperature is 650 ℃ of left and right.Compare with low-temperature fuel cell, high-temperature fuel cell has obvious advantage: (1) can be used fossil fuel, and fuel reforming temperature is higher, and battery that can be higher with temperature is realized thermal coupling, even can directly at inside battery, carry out the reformation of fuel, system is simplified; (2) used heat that the battery that temperature is higher produces has higher value, can realize cogeneration; (3) under low temperature, CO easily makes catalyst poisoning, and at high temperature, CO is but a kind of fuel; (4), under higher temperature, the oxidation reaction of hydrogen and the reduction reaction of oxygen are active enough high, do not need to use noble metal as eelctro-catalyst; (5) in cell reaction, charge carrier does not need water as medium, has avoided the water management system of low temperature battery complexity; (6) in MCFC, CO
2as a kind of cathode inlet, consume, this (is mainly CO for current minimizing greenhouse gas
2) discharge there is important environment protection significance.
At present, the business-like subject matter of restriction MCFC is life problems.Current MCFC can only reach 2～30,000 hours, from its commercialization, requires to also have for 40,000 hours certain distance.The reason that affects the MCFC life-span mainly contains cathode dissolution, electrolytical volatilization loss, the problems such as membranes pores alligatoring and anode creep.Wherein, the storage of molten carbonate fuel cell electrolyte is the key factor that affects the MCFC life-span with a compensation difficult problem, and in order to accelerate the commercialization of MCFC, the scientific research institutions that are engaged in MCFC both at home and abroad are all attempting solving this difficult problem.Through consulting a large amount of documents and materials, the electrolytical save scheme of MCFC mainly contains following three kinds at present: 1, electrolyte is stored in the gas flow of battery, like this in battery temperature-rise period, after electrolyte melting, rely on capillary force to immerse in barrier film, this method implements comparatively easy, but fused salt is comparatively serious to the corrosion of battery runner, and due to the impact of air-flow, easily there is problem of non-uniform in fused salt in the process that immerses barrier film; 2, electrolyte is made and be similar to the salt film that barrier film is the same, the form that is similar to sandwich when assembled battery is superimposed and carries out, this scheme also has certain feasibility in the battery pile of monocell or smallest number, but when battery pile is larger, because making battery pile, salt film thickness can there is larger sedimentation, barrier film is easily ftractureed, thereby affects the operation of battery pile; 3, electrolyte and barrier film powder are mixed to the integrated substrate of preparation, this scheme implements porosity and the pore size distribution of more difficult control barrier film.
Summary of the invention
For solving above-mentioned problems of the prior art, the object of the present invention is to provide a kind of storage and compensation method of molten carbonate fuel cell electrolyte, when the electrode that employing the inventive method is prepared and barrier film carry out assembled battery, battery is in operation does not have the generation of gas blowby and gas leak phenomenon, and owing to having electrolytical compensating action, extended the useful life of battery.
In order to achieve the above object, the technical solution adopted in the present invention is:
The storage of molten carbonate fuel cell electrolyte and a compensation method, comprise the steps:
Step 1: prepare satisfactory electrode and barrier film, the porosity of electrode is 60%～80%, and the porosity of barrier film is 50%～60%;
Step 2: the Li that the mol ratio that calculating needs in prepared barrier film and the electrode duct after complete roasting is 62:38
2cO
3and K
2cO
3the quality of molten salt electrolyte;
Step 3: the Li that is 62:38 by the mol ratio of calculating gained quality
2cO
3and K
2cO
3molten salt electrolyte fully mixes and is dried processing, according to the quality of calculated molten salt electrolyte, molten salt electrolyte is layered on respectively on electrode and barrier film equably;
Step 4: the electrode and the barrier film that are placed with molten salt electrolyte are put into Muffle furnace, at 480～540 ℃, carry out roasting 10～20 hours, make to immerse in electrode and barrier film after electrolyte melting, so just the required electrolyte of molten carbonate fuel cell is stored in electrode and barrier film, until electrode and barrier film, just can carries out assembling and the test of battery after cooling.
Through above-mentioned steps process, in molten carbonate fuel cell power generation process, required fused electrolyte is just stored in electrode and barrier film, and in battery operation process, fused electrolyte in barrier film is because vaporization at high temperature can lose a part, and the fused electrolyte storing in electrode can compensate it in time, thus useful life and the performance of assurance molten carbonate fuel cell.
The anode aperture of described electrode is 3～7 μ m, and porosity is 60%～70%; Negative electrode aperture is 7～10 μ m, and porosity is 70%～80%.
The aperture of described barrier film is 0.1～1 μ m.
Described in step 2, calculate the Li that mol ratio is 62:38
2cO
3and K
2cO
3the method of the quality of molten salt electrolyte is: the porosity of first measuring prepared barrier film and electrode by mercury injection apparatus; According to the thickness of porosity and barrier film and electrode, area, just can calculate the pore volume of barrier film and electrode; With the pore volume of barrier film and electrode, be multiplied by the Li that mol ratio is 62:38 respectively
2cO
3-K
2cO
3salt-mixture density, obtain the quality of the molten salt electrolyte that needs in barrier film and the electrode duct after complete roasting.
The inventive method easy operating, to improving, the electrolyte of molten carbonate fuel cell stores and compensation aspect has important practical significance.When the electrode that employing the inventive method is prepared and barrier film carry out assembled battery, battery is in operation does not have the generation of gas blowby and gas leak phenomenon, and owing to having electrolytical compensating action, extended the useful life of battery.The present invention has important directive significance to improving the aspects such as useful life of battery performance and prolongation battery, to accelerating China, in the progress aspect MCFC, has important facilitation.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
Prepare electrode and barrier film, adopt mercury injection apparatus to measure the electrode of preparation and the porosity of barrier film, adopt vernier caliper and ruler to measure their thickness and area, after measured, the porosity of anode is 60%, and thickness is 0.8mm, and area is 233cm
2; The porosity of negative electrode is 70%, and thickness is 0.9mm, and area is 233cm
2; The porosity of barrier film is 50%, and thickness is 0.95mm, and area is 336cm
2.According to the porosity of anode, negative electrode and barrier film and thickness, area, just can calculate their pore volume; By pore volume, be multiplied by the Li that mol ratio is 62:38
2cO
3-K
2cO
3salt-mixture density (at present experience density is 2.23g/cm
3), so just can determine comparatively exactly the quality of required molten salt electrolyte.By calculating, the electrolyte quality that anode hole structure can store is 24.94g, and the amount of electrolyte that negative holes structure can store is 32.73g, and the required electrolyte quality of membranes pores structure is 35.59g.
The Li that is 62:38 by mol ratio
2cO
3-K
2cO
3electrolyte fully mixes and is dried processing, taking respectively 24.94g, 32.73g and 35.59g electrolyte is laid on anode, negative electrode and barrier film, in tiling process, must guarantee certain evenness and uniformity, then they are put into Muffle furnace and at 540 ℃, carry out roasting 10 hours, make to immerse in electrode and barrier film after electrolyte melting, until electrode and barrier film, just can carry out assembling and the test of battery after cooling.Through said process, in molten carbonate fuel cell power generation process, required electrolyte is just stored in electrode and barrier film, and in battery operation process, electrolyte in barrier film is because vaporization at high temperature can lose a part, and the electrolyte storing in electrode can compensate it in time, thus useful life and the performance of assurance molten carbonate fuel cell.
Embodiment 2
Prepare electrode and barrier film, adopt mercury injection apparatus to measure the electrode of preparation and the porosity of barrier film, adopt vernier caliper and ruler to measure their thickness and area, after measured, the porosity of anode is 70%, and thickness is 0.8mm, and area is 233cm
2; The porosity of negative electrode is 80%, and thickness is 0.9mm, and area is 233cm
2; The porosity of barrier film is 60%, and thickness is 0.95mm, and area is 336cm
2.According to the porosity of anode, negative electrode and barrier film and thickness, area, just can calculate their pore volume; By pore volume, be multiplied by the Li that mol ratio is 62:38
2cO
3-K
2cO
3salt-mixture density (at present experience density is 2.23g/cm
3), so just can determine comparatively exactly the quality of required molten salt electrolyte.By calculating, the electrolyte quality that anode hole structure can store is 29.10g, and the amount of electrolyte that negative holes structure can store is 37.41g, and the required electrolyte quality of membranes pores structure is 42.71g.
The Li that is 62:38 by mol ratio
2cO
3-K
2cO
3electrolyte fully mixes and is dried processing, taking respectively 29.10g, 37.41g and 42.71g electrolyte is laid on anode, negative electrode and barrier film, in tiling process, must guarantee certain evenness and uniformity, then they are put into Muffle furnace and at 480 ℃, carry out roasting 20 hours, make to immerse in electrode and barrier film after electrolyte melting, until electrode and barrier film, just can carry out assembling and the test of battery after cooling.Through said process, in molten carbonate fuel cell power generation process, required electrolyte is just stored in electrode and barrier film, and in battery operation process, electrolyte in barrier film is because vaporization at high temperature can lose a part, and the electrolyte storing in electrode can compensate it in time, thus useful life and the performance of assurance molten carbonate fuel cell.
Claims (4)
1. the storage of molten carbonate fuel cell electrolyte and a compensation method, is characterized in that, comprises the steps:
Step 1: prepare satisfactory electrode and barrier film, the porosity of electrode is 60%～80%, and the porosity of barrier film is 50%～60%;
Step 2: the Li that the mol ratio that calculating needs in prepared barrier film and the electrode duct after complete roasting is 62:38
2cO
3and K
2cO
3the quality of molten salt electrolyte;
Step 3: the Li that is 62:38 by the mol ratio of calculating gained quality
2cO
3and K
2cO
3molten salt electrolyte fully mixes and is dried processing, according to the quality of calculated molten salt electrolyte, molten salt electrolyte is layered on respectively on electrode and barrier film equably;
Step 4: the electrode and the barrier film that are placed with molten salt electrolyte are put into Muffle furnace, at 480～540 ℃, carry out roasting 10～20 hours, make to immerse in electrode and barrier film after electrolyte melting, so just the required electrolyte of molten carbonate fuel cell is stored in electrode and barrier film, until electrode and barrier film, just can carries out assembling and the test of battery after cooling.
2. the storage of a kind of molten carbonate fuel cell electrolyte according to claim 1 and compensation method, is characterized in that, the anode aperture of described electrode is 3～7 μ m, and porosity is 60%～70%; Negative electrode aperture is 7～10 μ m, and porosity is 70%～80%.
3. the storage of a kind of molten carbonate fuel cell electrolyte according to claim 1 and compensation method, is characterized in that, the aperture of described barrier film is 0.1～1 μ m.
4. the storage of a kind of molten carbonate fuel cell electrolyte according to claim 1 and compensation method, is characterized in that, calculates the Li that mol ratio is 62:38 described in step 2
2cO
3and K
2cO
3the method of the quality of molten salt electrolyte is: the porosity of first measuring prepared barrier film and electrode by mercury injection apparatus; According to the thickness of porosity and barrier film and electrode, area, just can calculate the pore volume of barrier film and electrode; With the pore volume of barrier film and electrode, be multiplied by the Li that mol ratio is 62:38 respectively
2cO
3-K
2cO
3salt-mixture density, obtain the quality of the molten salt electrolyte that needs in barrier film and the electrode duct after complete roasting.
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| CN201410304820.XA CN104078698B (en) | 2014-06-30 | 2014-06-30 | A kind of storage of molten carbonate fuel cell electrolyte and compensation method |
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| CN104078698B CN104078698B (en) | 2016-03-30 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110911717A (en) * | 2019-12-03 | 2020-03-24 | 中国华能集团清洁能源技术研究院有限公司 | Electrolyte supplementing method for molten carbonate fuel cell stack |
| CN112820923A (en) * | 2021-03-19 | 2021-05-18 | 华能国际电力股份有限公司 | Electrolyte adding method for molten carbonate fuel cell |
| CN112928318A (en) * | 2021-03-18 | 2021-06-08 | 华能国际电力股份有限公司 | Binderless molten carbonate fuel cell electrolyte membrane and preparation method thereof |
| CN114937807A (en) * | 2022-05-23 | 2022-08-23 | 江苏正力新能电池技术有限公司 | Lithium ion battery and power utilization device |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110911717A (en) * | 2019-12-03 | 2020-03-24 | 中国华能集团清洁能源技术研究院有限公司 | Electrolyte supplementing method for molten carbonate fuel cell stack |
| CN112928318A (en) * | 2021-03-18 | 2021-06-08 | 华能国际电力股份有限公司 | Binderless molten carbonate fuel cell electrolyte membrane and preparation method thereof |
| CN112820923A (en) * | 2021-03-19 | 2021-05-18 | 华能国际电力股份有限公司 | Electrolyte adding method for molten carbonate fuel cell |
| CN114937807A (en) * | 2022-05-23 | 2022-08-23 | 江苏正力新能电池技术有限公司 | Lithium ion battery and power utilization device |
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